Substances and method for the production of water suitable for aquariums or garden ponds

ABSTRACT

The present invention is concerned with agents and processes for the production of biologically advantageous to almost natural maintenance water, especially for aquaria and garden pond water and also from biologically unfavorable to harmful starting water.

DESCRIPTION

The present invention is concerned with agents and processes for theproduction of biologically advantageous to almost natural maintenancewater, especially for aquaria and garden pond water, also frombiologically unfavourable to harmful starting water.

In aquaria or in the maintenance of aquatic animals, for about 30 yearsit has become established practice partly or completely to exchange themaintenance water regularly by fresh water and thereby to reduce theloading of the maintenance water in relation to the water exchange rate.

Of the possible sources of fresh water, for example spring water,rainwater and tap water, tap water or drinking water has by far achievedthe greatest importance because of its outstanding purity.

However, in the case of the use of tap or drinking water as fresh waterfor aquaria, problems arise since tap or drinking water is speciallyprepared, having regard to its use as nutriment for humans, in the localwaterworks. Because of these special properties controlled by thedrinking water regulations, drinking water differs considerably fromnatural, bioactive waters in the following aspects:

it is almost germ-free;

it contains no or only negligible amounts of organic materials;

it contains non-complexed heavy metals which are admittedly completelyharmless for humans but which can be highly toxic for water organisms;

it is frequently mixed with disinfecting, degerminating compounds, forexample chlorine or other active chlorine compounds, in order to ensurethe hygienic character of the drinking water up to the final user;

the Ca:Mg ratio is often far too high and magnesium ions are oftencompletely absent;

in inland regions, the iodine content is extremely low;

the redox character is in the strongly oxidising region, already broughtabout by the presence of chlorine and active chlorine compounds;

because of the above-described properties and especially because of theabsence of organic compounds, it acts very aggressively on the sensitivemucous membranes of fish and other water organisms.

From all of the described properties of tap or drinking water, itfollows that, because of its purity, it admittedly appears to be verysuitable to improve loaded maintenance water by water exchange but thisinitially very positive aspect is nullified by the series ofabove-mentioned negative factors or is even reversed.

From DE 22 21 545, it is known to minimise or solve important aquarialproblems of tap or drinking water by means of functional syntheticadditives.

The problem of chlorine or active chlorine compounds can be solved bymeans of reduction by sodium thiosulphate.

Heavy metals can be removed by complexing with synthetic complexformers, for example ethylenediamine-tetraacetic acid (EDTA).

The aggressive behaviour of tap water can be ameliorated by the additionof polyvinylpyrrolidones.

The addition of vitamin B₁ has proved to be useful as an anti-stresscomponent.

The acute negative aspects of tap or drinking water are admittedly dealtwith, ameliorated or eliminated by these suggested agents but thesemeasures introduce new and unnatural materials into the almost naturalmaintenance system, the effects of which on biological processes are notprecisely known.

The biological decomposability of these synthetic compounds is also, asa rule, retarded or does not take place because of their xenobiotic(biologically foreign) nature.

It is known of EDTA and analogous compounds and of polyvinylpyrrolidonesthat they are not broken down at all or only very slowly. In the case ofthe use of thiosulphate as anti-chlorine reagent, depending upon thestoichiometry, there result further polysulphane-polysulphonic acids,for example tetrathionate, S₄O₆ ²⁻, and other reaction products, thebiological action of which is also not known. Thiosulphate and itscomplex subsequent products are biologically foreign and potentiallyharmful substances.

Summarising, it can be stated that the solutions to the problemsdescribed in DE 22 21 545 admittedly function satisfactorily from thechemical point of view but the biological effects thereof on the smallecosystems of aquaria and other maintenance systems is not known and,therefore, initially are to be regarded as being at most neutral.

With the present invention, it is achieved that all the above-describedproblems which arise in the case of the use of tap or drinking water forthe exchange of water in biological maintenance systems are reduced orovercome without it resulting in the introduction of biologically orecologically foreign materials into the maintenance systems, for exampleaquaria.

Surprisingly, all problems in the case of fresh tap or drinking watercan be solved by not using the above-described synthetic compounds butrather exclusively materials or compounds which occur naturally or areproduced in natural systems of organisms (vegetable and animal organismsand micro-organisms).

These materials are, in part, present as metabolic products in naturalwaters in steady state concentrations as the result of biologicalproduction and breakdown processes.

If the naturally occurring materials described in the present inventionare used in order to eliminate the negative aspects which are involvedwith the use of fresh tap water, then there are achieved all the desiredpositive effects of an exchange of water in the case of the addition offresh tap water to the maintenance system and thus the possibly damagingfactors which are involved with an exchange of water are eliminated.

After the chemical reaction of the added natural additives in the freshwater, as unused materials and subsequent products there are onlypresent compounds which can be broken down biologically withoutproblems.

In addition to the reduction of the harmful factors, the added naturalcompounds themselves or the reaction or breakdown products thereofmanifest further positive effects in the ecosystem, for example theaquarium.

The variant of the working up of biologically-ecologically unfavourabletap or drinking water, here presented as the solution according to thepresent invention, is novel and, in the totality of the positiveactions, is also surprising for the expert. For the first time, it ispossible to change sterile, aggressive tap or drinking water into almostnatural biologically-friendly maintenance water with the use of naturalactive materials and, parallel thereto, to permit the introduction offurther useful factors or to allow these to arise in biological ways.

In the following, the solutions of the problem according to the presentinvention are described on the basis of fresh water-problem factors formaintenance systems:

Natural reducing agents for chlorine and other active chlorinecompounds:

For this purpose, all natural materials can be used which themselves arenon-toxic and can be broken down biologically and manifest a reducingaction with regard to chlorine and other active chlorine compounds, forexample chloramine, chlorine dioxide and the like. Examples hereforinclude:

reducing carboxylic acids and the salts thereof, for example formic acidand oxalic acid;

natural compounds with aldehyde groups, for example, aldoses, uronicacids, such as erythrose, threose, arabinose, glucose, mannose,galactose, glucuronic acid, mannuronic acid and galacturonic acid;

compounds which contain thioether and thiohydroxy groups, for examplemethionine, cysteine, glutathione and D-penicillamine;

diverse natural reducing agents, for example ascorbic acid, tannic acidand tannins.

The concentrations used depend stoichiometrically on the concentrationsof the oxidising agents to be expected (chlorine and active chlorinecompounds) and are in the range of from 0.1-100 mg/1 and preferably offrom 0.5-20 mg/1.

Natural complex formers which can be used for reducing the heavy metaltoxicity admittedly mostly do not reach the extremely high complexformation constants of the synthetic complex formers, such as EDTA, DTPAand the like, but nevertheless also lead to a considerable lowering oreven elimination of the heavy metal toxicity especially also since,because of their high biocompatibility, they can also be used in largestoichiometric excess. By the formation of 2:1 and 3:1 complexes (witheven still higher ratios) (in contradistinction to the 1:1 complexes ofthe synthetic complex formers), there are also achieved sufficientlyhigh masking effects of the toxic metals and thus an effectivedetoxification with regard to water organisms.

A further advantage of the natural complex formers is the goodbiological decomposability of the ligands. During the breakdown, itautomatically results in an incorporation and immobilisation of thetoxic central metal ions in the decomposing micro-organisms and therebyresults in a removal of the toxic metals dissolved in the water.

This is in positive contradistinction to the detoxification with EDTAand analogous compounds, the metal complexes of which are biologicallyonly broken down very slowly and, therefore, are present in the water indissolved form for a long time.

Examples of natural complex formers include:

organic carboxylic acids and salts thereof with 2- and multi-toothedligand properties, for example oxalic acid, tartaric acid, citric acid,mono- and dicarboxylic acids of trioses, tetroses, pentoses, hexoses,for example gluconic acid, mannonic acid, D-sugar acids, mannosugaracids, mucic acid;

polymers with carboxyl groups, for example alginic acid and alginates,polyglucuronic acid (hemicellulose), gum arabic, ghatti gum, gumtragacanth, pectines and xanthan.

The mol weights of the natural biopolymers lie in the following ranges:

alginic acid, alginates 100,000-500,000 D polyglucuronic acid50,000-500,000 D gum arabic 250,000-1,000,000 D ghatti gum100,000-1,000,000 D gum tragacanth up to 800,000 D pectins50,000-180,000 D xanthan 100,000-1,000,000 D

Amino acids, for example glycine, alanine, valine, leucine, isoleucine,phenylalanine, tyrosine, proline, hydroxyproline and tryptophane andespecially serine, threonine, cysteine, methionine, aspartic acid,glutamic acid, arginine, lysine, histidine and ornithine.

Natural complex formers, for example L-dopa and D-penicillamine

Naturally-occurring phenyl-carboxylic acids, for example hydroxybenzoicacid and hydroxysinnamic acid derivatives, for example gallic acid,gallotannins, chlorogenic acid, caffeic acid and quinic acid.

Natural humic acids and fulvic acids obtained from humus materials inthe soil, from peat, from waters, as well as tannic acids and tannins.

Naturally-occurring porphyrin systems or porphyrin coloured materials,for example chlorophylls (Mg²⁺ complexes) which can also be usedsaponified or demetalised without the central metal.

Bile coloured materials, for example bilirubin.

Natural peptides and proteins, for example glutathione, casein, albuminand lactalbumin.

The concentrations of use of the natural complex formers depend upon theexpected and prevailing heavy metal concentrations in the drinking waterand are in the range of from 0.1-100 mg/1 and preferably of from 1-20mg/1.

Natural hydro-/biocolloids for reducing the aggressiveness of tap waterand for the protection of the mucous membranes of water organisms.

Instead of the synthetic hydrocolloids PVP and cellulose derivative,hydrocolloids which are formed by plants, algae and micro-organisms canalso very well be used.

Vegetable hydrocolloids, for example guar gum, gum arabic, ghatti gum,karaya gum, gum tragacanth, carob gum, pectins, dextrins and tamarindgum.

The mol weights of the vegetable hydrocolloids lie in the followingranges:

guar gum 100,000-1,000,000 D gum arabic 100,000-1,000,000 D ghatti gum100,000-1,000,000 D karaya gum 100,000-1,000,000 D gum tragacanth100,000-1,000,000 D carob gum 100,000-1,000,000 D pectins100,000-1,000,000 D tamarind gum 50,000-120,000 D dextrins50,000-500,000 D

Hydrocolloids produced by algae, for example alginic acid, alginates,carrageenan, furcelleran, agar-agar and Danish agar.

The mol weights of the hydrocolloids produced by algae lie in thefollowing ranges:

alginic acid, alginates 100,000-500,000 D carrageenan 50,000-500,000 Dfurcelleran 50,000-500,000 D agar-agar 50,000-500,000 D Danish agar50,000-500,000 D

Colloids produced by micro-organisms, for example xanthan gum,scleroglucan, curdlan (succinoglucan) and pullulan.

The mol weights of the biocolloids produced by micro-organisms lie inthe following ranges:

xanthan gum 100,000-1,000,000 D scleroglucan 50,000-500,000 D curdlan(succinoglucan) 50,000-500,000 D pullulan 50,000-500,000 D

The concentrations of use of the biocolloids are from 0.1-100 mg/1 andpreferably from 1-20 mg/1.

Further usable cell-protecting, bacteria-promoting and ecologicallyadvantageous compounds:

Besides the substances already defined and set out above which, inaddition to their functional task role, also promote the bioactivemicro-organisms because of their easy biological decomposability, thereis a series of natural compounds which have proved to be generallyprotective, for example against chemical and osmotic level variations.

An addition of such materials to a drinking water conditioning productdisplays cell- and organism-protecting functions especially in the caseof stress caused by the change of water.

The following compounds can be used for these purposes:

carbohydrates, for example the disaccharides saccharose, lactose,maltose, sucrose and trehalose, as well as polysaccharides, for examplepectins, hemicellulose, dextrins and xylans.

The mol weights of the biopolymers lie in the following ranges:

pectins (hemicelluloses) 50,000-180,000 D dextrins 50,000-500,000 Dxylans 50,000-500,000 D

Monomeric sugars, for example glucose, fructose, mannose, galactose,ribose, arabinose, erythrose and threose;

sugar alcohols, for example glycerol, sorbitol, erythritol, mannitol andinositol;

amino acids as set out above under complex formers;

natural betaines, for example betaine (trimethyl-glycine).

The concentrations of use lie in the range of from 0.1-100 mg/1 andpreferably of from 5-20 mg/1.

Correction additives for the approximation of the chemical properties oftap and drinking water, spring water and rain water to the conditions ofnatural waters can also be used in the compositions according to thepresent invention. There here comes into consideration especially theaddition of magnesium salts.

A deficiency of magnesium salts or even the absence thereof in the freshwaters used or the usually prevailing high Ca:Mg ratio can be correctedby the addition of magnesium salts. It is thereby advantageous to use atleast in part magnesium salts of the above- described carboxylic acids,amino acids, humic and fulvic acids employed according to the presentinvention, as well as porphyrin complexes (chlorophylls), in order tominimise the introduction of magnesium salts of more common anions, forexample chloride or sulphate.

Therefore, there can be used:

magnesium salts of carboxylic acids, amino acids, humic and fulvic acidsused according to the present invention;

magnesium complexes (as chlorophylls);

magnesium chloride or sulphate in the smallest possible amounts.

The concentrations of use in the fresh water should be from 0.5-100 mg/1of magnesium ions and preferably 1-10 mg/1 of magnesium ions.

A further correction additive consists in the addition of iodides. Thelack of iodine occurring very frequently inland in tap and drinkingwater can be compensated for by the addition of iodides or iodates, forexample sodium iodide, potassium iodide and potassium iodate, to thefresh water.

The concentrations of use in the supplemented fresh water should be from1 to 100 μg/1 of iodide and preferably from 5 to 20 μg/1 of iodide orfrom 1.5 to 140 μg/1 of iodate and preferably of from 7 to 28 μg/1 ofiodate.

The solutions of the individual problems according to the presentinvention described above can be used not only individually or combinedor also more advantageously in the combination of all individual problemsolutions for the natural water preparation of tap and drinking waters.

The substances listed under each individual problem solution are to beused individually or in combination, whereby the sum of the individualsubstance concentrations, i.e. their total concentration, should, ineach case, reach the given concentration limits.

The described individual problem solutions or substance or functiongroups, as described above, are used for the natural water preparationof tap or drinking water. To the portion of fresh water (of tap ordrinking water) is thereby added a final product which introduces thevarious groups of substances in the given concentrations.

It is also possible to refer the dosaging of the fresh waterconditioning product to the total amount of maintenance water(non-changed amount plus exchanged amount of fresh water).

A further method for the obtaining of a biologically active,substantially natural maintenance water is the frequent periodicaldosing in, for example daily, every 2 or 3 days or weekly, of the waterconditioning agent in correspondingly smaller dosaging. Due tocontinuous dosing in and rapid biological breakdown, low steady stateconcentrations of the individual components are achieved.

However, this kind of quasi-continuous dosing in is less suitable forthe supplementation of magnesium in which it is a matter of a rapidincreasing of the initial concentration.

The above-described combination products can be used in various forms ofadministration, namely, not only in the form of liquid products, forexample aqueous solutions, but also in the form of solid compositions,for example as tablets, powder mixtures, granulates, extrudates,capsules and the like.

The total amount of active substances or the amount of product in thecase of a given concentration of active substances determines theproduct range, i.e. the amount of water to be treated.

In addition to the components according to the present invention, thefinal products can contain further formulation components known to theexpert from the prior art, for example synthetic working-up components,such as are described in DE 22 21 545, buffers, if possible of a naturalbasis, preserving agents, colouring materials, odour and flavouringmaterials and/or thickening agents. The following Examples are given forthe purpose of illustrating the present invention:

EXAMPLE 1

Product with partial function which, after addition to the maintenancewater/fresh water, adjusts the following concentrations of thefunctional components:

tartaric acid 30 μmol/l formate 50 μmol/l magnesium ions 8 mg/l.

EXAMPLE 2

Product with complete function batch containing all functions accordingto the present invention which, after addition to the maintenancewater/fresh water, adjusts the following concentrations of naturalfunctional components:

citric acid 40 μmol/l glutamic acid 10 μmol/l formate 40 μmol/1 xanthan0.5 mg/l gum arabic 1.0 mg/l pectin 0.5 mg/l agar-agar 1.0 mg/lmagnesium ions 5 mg/l iodide ions 20 μg/l betaine 2 mg/l.

EXAMPLE 3

Product with complete batch of natural functions as described in Example2 and additionally containing components according to the prior art (DE22 21 545) for the strengthening of specific functions. In the case ofrecommended dosaging, the following end concentrations are achieved inthe maintenance water/fresh water:

ethylenediamine-tetraacetate 10 μmol/l citric acid 40 μmol/l glutamicacid 20 μmol/l formate 40 μmol/l polyvinylpyrrolidone 3 mg/lhydroxyethylcellulose 1 mg/l xanthan 1 mg/l gum arabic 1 mg/l pectin 1mg/l agar-agar 1 mg/l magnesium ions 8 mg/l iodide ions 10 μg/l betaine2 mg/l

The advantages of the working-up agents according to the presentinvention are considerable. In comparison with products according to theprior art, by combination of exclusively or preponderantlynaturally-occurring active substances, the following product functionsare achieved individually or in combination:

reduction of chlorine and of other active chlorine substances;

complexing of toxic heavy metals and reduction of the metal toxicity;

reduction of the aggressiveness of tap water and mucous membraneprotection;

cell protection, promotion of the bacteria and of the ecosystem;

supplementation of the content of magnesium and iodide ions.

Further advantages of the use of natural substances are:

easy microbial decomposability;

after fulfilment of their function, the active materials achieve shortresidence times in the maintenance water;

in the case of breakdown, plant-promoting materials are formed, mainlycarbon dioxide;

very good compatibility for all animal and plant water organisms;

no accumulation in the case of repeated use;

can also be used between water changes; and

quasi-continuous, under-dosed use produces low steady-stateconcentrations of the important natural active materials.

What is claimed is:
 1. An agent for reducing the negative or harmfuleffects of to aquatic animal life of water treated and/or purified forhuman or animal consumption, comprising: a) correction additives for theapproximation of natural water quality; and b) a natural additivecomprising tartaric acid, formate and magnesium ions.
 2. An agentaccording to claim 1, additionally containingethylenediamine-tetraacetate, polyvinylpyrrolidone andhydroxyethylcellulose.
 3. An agent according to claim 1, wherein it isprepared as a concentrated aqueous solution.
 4. An agent according toclaim 1, wherein it is preparedin the form of tablets, powder mixtures,granulates, extrudates or capsules.
 5. An agent according to claim 4,wherein it is confectioned as an individual dose for treatment of adefinite amount of water.